CN105542363B - A kind of preparation method of bi-directional synchronization stretching PVDF based coextruded films - Google Patents
A kind of preparation method of bi-directional synchronization stretching PVDF based coextruded films Download PDFInfo
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- CN105542363B CN105542363B CN201610055048.1A CN201610055048A CN105542363B CN 105542363 B CN105542363 B CN 105542363B CN 201610055048 A CN201610055048 A CN 201610055048A CN 105542363 B CN105542363 B CN 105542363B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention discloses a kind of preparation method of bi-directional synchronization stretching PVDF based coextruded films, and it is 5~9 mainly by mass fraction ratio：1~5 PVDF is with after compatible polymeric resin drying process, being placed in 100~250 DEG C of 10~60min of melt blending in kneading machine, obtaining uniform blend composition；Again by blend composition be placed on vulcanizing press it is hot-forming after be immediately placed in 0 DEG C of mixture of ice and water and quenched, then 2~10h is dried under conditions of 20~80 DEG C, obtains bi-directional synchronization stretched sheet；Sheet material is placed on bi-directional synchronization stretching-machine, preheats 160~250 DEG C, 5~60min, rate of extension is 15~50mm/s, and draw ratio is 2~4, obtains the PVDF based coextruded films that thickness is 5 50 μm after natural cooling in atmosphere.Present invention process and equipment are relatively easy, and cost is low, green, easy large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of laminated film.
Background technology
In recent years, with the development of electronic and electrical industry and the demand of convenient reliable electronic energy system, there is high storage
Energy density, low-loss polymeric dielectric film have obtained increasing concern.In the polymer having now been found that, PVDF
And its copolymer has higher dielectric constant (about 10), its electric breakdown strength and BOPP are similar, and have good mechanics
Performance, corrosion-resistant, high temperature resistant and radiation resistance.Currently used high-voltage capacitor mainly uses BOPP as thin dielectric
Film, although have very high electric breakdown field strength (>700MV/m), but due to its dielectric constant very it is low (<3), its energy storage density also compared with
Low (<3J/cm3).Therefore, on the premise of thin-film dielectric constant is not significantly reduced, the energy storage of laminated film is improved as far as possible
Density turns into the focus and difficult point of correlative study.
At present, the method for preparing high energy storage density PVDF and its copolymer matrix film typically uses solution cast film formation.
Solution cast film formation process conditions require high, and solvent for use environmental pollution is serious, complex process, is unfavorable for extensive life
Production.And when using bi-directional synchronization stretching to PVDF and its copolymer processing, because PVDF and its copolymer crystalline rate are fast, crystallize
Degree is higher so that necking penomena easily occurs in drawing process in film, causes uneven film thickness, or even rupture.
The content of the invention
The invention provides a kind of bi-directional synchronization of high energy storage density that is green, can preparing on a large scale to stretch PVDF bases
The preparation method of laminated film.The purpose of the present invention is by adding fluoropolymer resin compatible in PVDF, reducing
PVDF crystalline rate and crystallinity, prepare the more excellent bi-directional synchronization stretching PVDF based coextruded films of energy storage density.
The preparation method of the present invention is as follows：
(1) raw material：The mass fraction ratio of PVDF and compatible polymeric resin is 5~9：1~5；
The compatible polymeric resin includes：PS, PVP, PVC, PMMA, PP or PE；
PVDF resin melts flowing speed is 3~8g/10min (12.5Kg/230 DEG C), the compatible polymeric tree
Fat melt flow rate (MFR) is 3~10g/10min (3.8Kg/230 DEG C)；
(2) drying process：PVDF and compatible polymeric resin are put into baking oven, 10~20h is dried at 50~70 DEG C；
(3) melt blending：The PVDF and compatible polymeric resin that step (2) is treated are placed in melt blending in kneading machine
10~60min, 100~250 DEG C of mixture temperature, rotating speed are 20~80r/min, obtain uniform blend composition；
(4) preparation of bi-directional synchronization stretched sheet：The blend composition that step (3) obtains is placed on vulcanizing press and is hot pressed into
Type, pressure are 0~15MPa, and molding temperature is 150~210 DEG C, 10~60min of pressing time, is immediately placed in 0 DEG C of ice afterwards
Quenched in aqueous mixtures, then 2~10h is dried under conditions of 20~80 DEG C, it is 100~600 μm two-way to obtain thickness
Synchro-draw sheet material；
(5) preparation of bi-directional synchronization oriented film：The sheet material that step (4) obtains is placed on bi-directional synchronization stretching-machine, in advance
Hot temperature is 160~250 DEG C, and preheating time is 5~60min, and rate of extension is 15~50mm/s, and draw ratio is 2~4, in sky
The PVDF based coextruded films that thickness is 5-50 μm are obtained in gas after natural cooling.
The present invention has the following advantages that compared with prior art：
1st, technique and equipment are relatively easy, and cost is low, green, can prepare on a large scale.
2nd, PVDF crystalline rate and crystallinity can be reduced, so as to reduce processing temperature during bi-directional synchronization stretching.
3rd, thickness is uniform, and its energy storage density is up to 17.7J/cm3。
Brief description of the drawings
Fig. 1 is the two-way ferroelectric hysteresis loop curve map of laminated film prepared by the embodiment of the present invention 1,2,3.
Fig. 2 is the unidirectional ferroelectric hysteresis loop curve map of laminated film prepared by the embodiment of the present invention 1,2,3.
Fig. 3 is the energy storage density curve map of laminated film prepared by the embodiment of the present invention 1,2,3.
Embodiment
Embodiment 1
By PVDF resins 90g, (French Acker agate, melt flow rate (MFR) are 3~8g/10min (ASTM D1238 12.5Kg/
230 DEG C)), (TaiWan, China, melt flow rate (MFR) are 3~10g/10min (ASTM to compatible polymeric resin (PMMA) 10g
D1238 3.8Kg/230 DEG C)) it is put into baking oven, 20h is dried at 50 DEG C；Melt blending 10min in kneading machine is subsequently placed in,
100 DEG C of mixture temperature, rotating speed 80r/min, obtains uniform blend composition；
Obtained homogeneous blend material is placed in hot-forming on vulcanizing press, pressure 3MPa, molding temperature 150
DEG C, pressing time 30min, it is immediately placed in 0 DEG C of mixture of ice and water and is quenched afterwards, then is dried under conditions of 20 DEG C
10h, it is 400 μm of bi-directional synchronization stretched sheets to obtain thickness；
Obtained sheet material is placed on bi-directional synchronization stretching-machine, preheating temperature is 160 DEG C, preheating time 60min, stretching
Speed is 15mm/s, and draw ratio 2, it is 50 μm of PVDF based coextruded films to obtain thickness after natural cooling in atmosphere, uses ion
Sputter is in the two sides metal spraying electrode of polymer composite film, the ferroelectric hysteresis loop of test compound film.
As shown in figure 1, compared with PVDF, the residual polarization of the film and coercive electric field substantially reduce.
As shown in Fig. 2 compared with PVDF, the electric breakdown field strength of the film is significantly increased, and residual polarization is decreased obviously.
As shown in Figure 3, it is known that the electric breakdown field strength of the laminated film is 575MV/m, energy storage density 17.7J/cm3。
Embodiment 2
By PVDF resins 70g, (French Acker agate, melt flow rate (MFR) are 3~8g/10min (ASTM D1238 12.5Kg/
230 DEG C)), (TaiWan, China, melt flow rate (MFR) are 3~10g/10min (ASTM D1238 to compatible polymeric resin (PVC) 30g
3.8Kg/230 DEG C)) it is put into baking oven, 15h is dried at 60 DEG C；It is subsequently placed in melt blending 30min in kneading machine, batch mixing temperature
180 DEG C of degree, rotating speed 50r/min, obtains uniform blend composition；
Obtained homogeneous blend material is placed in hot-forming on vulcanizing press, pressure 5MPa, molding temperature 180
DEG C, pressing time 40min, it is immediately placed in 0 DEG C of mixture of ice and water and is quenched afterwards, then is dried under conditions of 50 DEG C
6h, it is 100 μm of bi-directional synchronization stretched sheets to obtain thickness；
Obtained sheet material is placed on bi-directional synchronization stretching-machine, preheating temperature is 200 DEG C, preheating time 35min, stretching
Speed is 30mm/s, and draw ratio 3, it is 30 μm of PVDF based coextruded films to obtain thickness after natural cooling in atmosphere, uses ion
Sputter is in the two sides metal spraying electrode of polymer composite film, the ferroelectric hysteresis loop of test compound film.
As shown in figure 1, compared with PVDF, the residual polarization of the film and coercive electric field substantially reduce.
As shown in Fig. 2 compared with PVDF, the electric breakdown field strength of the film be increased, and residual polarization is decreased obviously.
As shown in Figure 3, it is known that the electric breakdown field strength of the laminated film is 500MV/m, energy storage density 11.6J/cm3。
Embodiment 3
By PVDF resins 60g, (French Acker agate, melt flow rate (MFR) are 3~8g/10min (ASTM D1238 12.5Kg/
230 DEG C)), (TaiWan, China, melt flow rate (MFR) are 3~10g/10min (ASTM D1238 to compatible polymeric resin (PVP) 40g
3.8Kg/230 DEG C)) it is put into baking oven, 10h is dried at 70 DEG C；It is subsequently placed in melt blending 60min in kneading machine, batch mixing temperature
250 DEG C of degree, rotating speed 20r/min, obtains uniform blend composition；
Obtained homogeneous blend material is placed in hot-forming on vulcanizing press, pressure 10MPa, molding temperature 210
DEG C, pressing time 10min, it is immediately placed in 0 DEG C of mixture of ice and water and is quenched afterwards, then is dried under conditions of 80 DEG C
2h, it is 600 μm of bi-directional synchronization stretched sheets to obtain thickness；
Obtained sheet material is placed on bi-directional synchronization stretching-machine, preheating temperature is 250 DEG C, preheating time 5min, stretching
Speed is 50mm/s, and draw ratio 4, it is 5 μm of PVDF based coextruded films to obtain thickness after natural cooling in atmosphere, uses ion
Sputter is in the two sides metal spraying electrode of polymer composite film, the ferroelectric hysteresis loop of test compound film.
As shown in figure 1, compared with PVDF, the residual polarization of the film and coercive electric field substantially reduce.
As shown in Fig. 2 compared with PVDF, the electric breakdown field strength of the film be increased, and residual polarization is decreased obviously, pole
Change and be intended to linear relationship with the curve of electric-field intensity.
As shown in Figure 3, it is known that the electric breakdown field strength of the laminated film is 375MV/m, energy storage density 8.5J/cm3。
Embodiment 4
By PVDF resins 50g, (French Acker agate, melt flow rate (MFR) are 3~8g/10min (ASTM D1238 12.5Kg/
230 DEG C)), (TaiWan, China, melt flow rate (MFR) are 3~10g/10min (ASTM D1238 to compatible polymeric resin (PS) 50g
3.8Kg/230 DEG C)) it is put into baking oven, 18h is dried at 65 DEG C；It is subsequently placed in melt blending 50min in kneading machine, batch mixing temperature
230 DEG C of degree, rotating speed 40r/min, obtains uniform blend composition；
Obtained homogeneous blend material is placed in hot-forming on vulcanizing press, pressure 15MPa, molding temperature 200
DEG C, pressing time 20min, it is immediately placed in 0 DEG C of mixture of ice and water and is quenched afterwards, then is dried under conditions of 60 DEG C
4h, it is 300 μm of bi-directional synchronization stretched sheets to obtain thickness；
Obtained sheet material is placed on bi-directional synchronization stretching-machine, preheating temperature is 180 DEG C, preheating time 15min, stretching
Speed is 20mm/s, and draw ratio 4, it is 10 μm of PVDF based coextruded films to obtain thickness after natural cooling in atmosphere, uses ion
Sputter is in the two sides metal spraying electrode of polymer composite film, the ferroelectric hysteresis loop of test compound film.
As shown in figure 1, compared with PVDF, the residual polarization of the film and coercive electric field substantially reduce.
As shown in Fig. 2 compared with PVDF, the electric breakdown field strength of the film substantially increases, and residual polarization is decreased obviously.
As shown in Figure 3, it is known that the electric breakdown field strength of the laminated film is 450MV/m, energy storage density 12.2J/cm3。
Claims (3)
- A kind of 1. preparation method of bi-directional synchronization stretching PVDF based coextruded films, it is characterised in that：(1) raw material：The mass fraction ratio of PVDF and compatible polymeric resin is 5~9：1~5；(2) drying process：PVDF and compatible polymeric resin are put into baking oven, 10~20h is dried at 50~70 DEG C；(3) melt blending：By step (2) treat PVDF and compatible polymeric resin be placed in melt blending 10 in kneading machine~ 60min, 100~250 DEG C of mixture temperature, rotating speed are 20~80r/min, obtain uniform blend composition；(4) preparation of bi-directional synchronization stretched sheet：The blend composition that step (3) obtains is placed in it is hot-forming on vulcanizing press, Pressure is 0~15MPa, and molding temperature is 150~210 DEG C, 10~60min of pressing time, is immediately placed in 0 DEG C of frozen water afterwards and mixes Quenched in compound, then 2~10h is dried under conditions of 20~80 DEG C, obtain the bi-directional synchronization that thickness is 100~600 μm Stretched sheet；(5) preparation of bi-directional synchronization oriented film：The sheet material that step (4) obtains is placed on bi-directional synchronization stretching-machine, preheating temperature Spend for 160~250 DEG C, preheating time is 5~60min, and rate of extension is 15~50mm/s, and draw ratio is 2~4, in atmosphere The PVDF based coextruded films that thickness is 5-50 μm are obtained after natural cooling.
- 2. the preparation method of bi-directional synchronization stretching PVDF based coextruded films according to claim 1, it is characterised in that：It is described Compatible polymeric resin includes：PS, PVP, PVC, PMMA, PP or PE.
- 3. the preparation method of bi-directional synchronization stretching PVDF based coextruded films according to claim 1, it is characterised in that：It is described PVDF resin melts flowing speed is 3~8g/10min, 12.5Kg/230 DEG C, and the compatible polymeric resin melt flows speed For 3~10g/10min, 3.8Kg/230 DEG C.
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| CN108948398A (en) * | 2018-07-20 | 2018-12-07 | 西南科技大学 | A kind of flexible piezoelectric laminated film and preparation method thereof |
| CN110229448B (en) * | 2019-06-26 | 2021-12-10 | 四川大学 | Method for preparing high-performance and multifunctional shape memory material |
| CN111303549B (en) * | 2020-04-07 | 2021-10-08 | 四川大学 | Preparation method of reinforced and toughened polystyrene and stretched film |
| CN113183576B (en) * | 2021-04-15 | 2023-05-26 | 西安交通大学 | Ordered mesostructure PVDF-PMMA blend film and preparation system thereof |
| CN114103348B (en) * | 2021-11-22 | 2023-03-14 | 四川大学 | Multilayer composite BOPE capacitor film and preparation method thereof |
| CN114989464B (en) * | 2022-06-02 | 2024-02-13 | 华东师范大学 | PVDF/PMMA composite film and preparation method thereof |
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| CN1554695A (en) * | 2003-12-24 | 2004-12-15 | 中国科学院广州化学研究所 | Process for preparing polymer diaphragm for lithium ion cell |
| CN101696309A (en) * | 2009-10-13 | 2010-04-21 | 常熟市冠日新材料有限公司 | Fluorine-contained film and preparation method thereof |
| CN103242660A (en) * | 2013-05-27 | 2013-08-14 | 刘江萍 | Preparation method of high-dielectric film |
| CN103878897A (en) * | 2014-01-06 | 2014-06-25 | 四川大学 | Method for preparing polymer blending material |
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Patent Citations (4)
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| CN1554695A (en) * | 2003-12-24 | 2004-12-15 | 中国科学院广州化学研究所 | Process for preparing polymer diaphragm for lithium ion cell |
| CN101696309A (en) * | 2009-10-13 | 2010-04-21 | 常熟市冠日新材料有限公司 | Fluorine-contained film and preparation method thereof |
| CN103242660A (en) * | 2013-05-27 | 2013-08-14 | 刘江萍 | Preparation method of high-dielectric film |
| CN103878897A (en) * | 2014-01-06 | 2014-06-25 | 四川大学 | Method for preparing polymer blending material |
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